CN112409970A - Bio-based epoxy resin composition containing silicon phenylene structure and application of bio-based epoxy resin composition in preparation of epoxy resin adhesive film - Google Patents
Bio-based epoxy resin composition containing silicon phenylene structure and application of bio-based epoxy resin composition in preparation of epoxy resin adhesive film Download PDFInfo
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- CN112409970A CN112409970A CN202011263948.8A CN202011263948A CN112409970A CN 112409970 A CN112409970 A CN 112409970A CN 202011263948 A CN202011263948 A CN 202011263948A CN 112409970 A CN112409970 A CN 112409970A
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- epoxy resin
- bio
- silicon
- based epoxy
- resin composition
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 158
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 158
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 59
- 239000010703 silicon Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000002313 adhesive film Substances 0.000 title claims abstract description 44
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 100
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 52
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000005770 Eugenol Substances 0.000 claims abstract description 51
- 229960002217 eugenol Drugs 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 20
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 56
- 238000001723 curing Methods 0.000 claims description 37
- 239000002994 raw material Substances 0.000 claims description 29
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052621 halloysite Inorganic materials 0.000 claims description 21
- 239000002071 nanotube Substances 0.000 claims description 21
- 229920000459 Nitrile rubber Polymers 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- UHXCHUWSQRLZJS-UHFFFAOYSA-N (4-dimethylsilylidenecyclohexa-2,5-dien-1-ylidene)-dimethylsilane Chemical compound C[Si](C)C1=CC=C([Si](C)C)C=C1 UHXCHUWSQRLZJS-UHFFFAOYSA-N 0.000 claims description 8
- -1 phenolic aldehyde amine Chemical class 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 238000002955 isolation Methods 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920006332 epoxy adhesive Polymers 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 12
- 239000003063 flame retardant Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
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- 229910052751 metal Inorganic materials 0.000 abstract description 2
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- 150000002739 metals Chemical class 0.000 abstract description 2
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- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003292 glue Substances 0.000 description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 25
- 229910052801 chlorine Inorganic materials 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000011410 subtraction method Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VVNBOKHXEBSBQJ-UHFFFAOYSA-M dodecyl(triethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](CC)(CC)CC VVNBOKHXEBSBQJ-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
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- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- QNVSXXGDAPORNA-UHFFFAOYSA-N Resveratrol Natural products OC1=CC=CC(C=CC=2C=C(O)C(O)=CC=2)=C1 QNVSXXGDAPORNA-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- DHKQQCXJDHXTOV-UHFFFAOYSA-M [NH4+].[Br-].[Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C Chemical compound [NH4+].[Br-].[Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C DHKQQCXJDHXTOV-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
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- 238000013475 authorization Methods 0.000 description 1
- AFAXLUGRHMPOFH-UHFFFAOYSA-M azanium dodecyl(trimethyl)azanium dibromide Chemical compound [NH4+].[Br-].[Br-].CCCCCCCCCCCC[N+](C)(C)C AFAXLUGRHMPOFH-UHFFFAOYSA-M 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
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- C09J7/00—Adhesives in the form of films or foils
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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Abstract
The invention relates to the technical field of synthesis and preparation of high polymer materials, and particularly discloses a bio-based epoxy resin composition containing a silicon phenylene structure and application thereof in preparation of an epoxy resin adhesive film. The bio-based epoxy resin composition containing the silicon phenylene structure is prepared by taking a bio-based epoxy resin with a novel structure as a matrix through a special catalyst and a solid alkali adding method, the bio-based epoxy resin is eugenol bio-based epoxy resin containing the silicon phenylene structure, the main reaction functional group is eugenol epoxy group, and the intrinsic flame retardant property and the temperature resistance of the material can be greatly improved by introducing the silicon phenylene structure in a molecular framework. In addition, the introduction of heteroatom silicon reduces the viscosity of the system. The epoxy resin composition with the epoxy resin as the matrix resin can realize the flame retardance of the body without adding a flame retardant, so that the prepared epoxy resin adhesive film has outstanding flame retardance, toughness, temperature resistance and bonding performance, is suitable for structural adhesives, and is particularly suitable for bonding the surfaces of metals, composite materials and plastics.
Description
Technical Field
The invention relates to the technical field of synthesis and preparation of high polymer materials, in particular to a silicon-phenylene structure-containing bio-based epoxy resin composition and application thereof in preparation of an epoxy resin adhesive film.
Background
Epoxy resin is widely applied to the fields of coatings, adhesives, automobile parts and the like because of excellent chemical, electrical, heat resistance, bonding and mechanical properties, and is one of three thermosetting polymer materials. Currently, almost all commercial epoxy resins are derived from petroleum base, and bisphenol a type epoxy resins account for about 90% of the production. Bisphenol a is one of the most widely used industrial compounds in the world, but with the recent deep understanding of the biotoxicity of bisphenol a, many countries have made it clear that the use of bisphenol a in plastic packaging and containers for food is prohibited. Therefore, the preparation of epoxy resins from bio-based raw materials has become a focus of research in recent years.
Bisphenol a epoxy resin is easily burnt and cannot be extinguished by itself after leaving a fire, and its LOI value is only about 20%. In order to meet the requirements of the fields of electronic information, aerospace, transportation and the like on flame retardant materials, high flame retardance becomes a necessary property of high-performance epoxy resin. An effective method for preparing flame-retardant polymers is to add flame retardants into the polymers, but the problems of poor compatibility, poor processability, poor thermal stability, low mechanical properties and the like are usually brought about, and the application range of the epoxy resin is greatly influenced. In conclusion, the development of the bio-based epoxy resin with intrinsic flame retardance and high thermal stability is of great significance, and the requirements of fire safety and practicability are expected to be met.
In recent years, the literature reports biomass raw materials substituted for bisphenol a type epoxy resins, such as epoxidized vegetable oil, rosin, cardanol, resveratrol, and the like. For example, chinese patent document No. CN 104892858B discloses a high bio-based content epoxy resin composition, and a curing method and application thereof, wherein the high bio-based content epoxy resin composition uses epoxy vegetable oil and unsaturated bio-based dicarboxylic acid as main components, and the main raw materials are derived from bio-based renewable resources. However, the epoxy vegetable oil belongs to fatty chain epoxy, and a network structure has high flexibility after curing, so that the prepared epoxy resin has poor flame retardance and heat resistance. Further, as disclosed in chinese patent No. CN 102206324B, a full bio-based epoxy resin composition and a cured product thereof have excellent uv resistance and aging resistance using a rosin-based epoxy resin as a matrix, but rosin epoxy itself has an ester ring structure, so its intrinsic flame retardancy and dielectric properties are common.
Eugenol, also known as 2-methoxy-4- (2-propenyl) phenol, is a naturally occurring aromatic compound that is the major component in clove oil and is a colorless to pale yellow liquid at room temperature. In the aspect of scientific research, the eugenol is mainly used for antibacterial and pharmacological research, and the eugenol raw material is cheap and easy to obtain.
Chinese patent with the authorization number of CN 105924623B discloses eugenol epoxy resin and a preparation method and application thereof, wherein eugenol is used as a raw material, and the specific preparation process comprises the following steps: a. condensation, namely catalyzing 100 parts by weight of eugenol and 75-300 parts by weight of halogenated propylene oxide by 0.1-2 parts by weight of phase transfer catalyst in the presence of 25-50 parts by weight of alkali to perform condensation reaction, and extracting, washing and drying the obtained reaction solution to obtain a condensation compound; b. and (2) oxidizing, namely dissolving the condensation compound in dichloromethane, oxidizing the condensation compound by using peroxide at the temperature of 0-30 ℃ for 24-72 hours, and then extracting, drying and decompressing the obtained reaction liquid to remove the solvent to obtain the eugenol epoxy resin. The phase transfer catalyst adopted in the technical scheme is aliphatic ammonium halide, and is specifically selected from at least one of tetramethylammonium chloride, tetrabutylammonium bromide, dodecyltrimethylammonium ammonium bromide and hexadecyltrimethylammonium ammonium bromide.
The patent literature also indicates that the eugenol epoxy resin prepared by the method has high epoxy value, and can replace bisphenol A epoxy resin to be applied to preparation of composite materials, coatings and adhesives. However, the literature does not give any performance data in the specific fields in which the above-mentioned materials are applied, and meanwhile, the reactant obtained in the preparation method needs repeated extraction and washing, waste liquid is generated more, the yield of the ring-closed product is low, about 70%, the content of hydrolyzable chlorine in the product is high, and the requirement of high-quality application is difficult to meet.
Disclosure of Invention
(1) Objects of the invention
The invention aims to provide a silicon-containing phenylene structure-containing bio-based epoxy resin composition, which takes bio-based epoxy resin with a novel structure as matrix resin, and an epoxy resin adhesive film prepared from the composition has the advantages of intrinsic flame retardance, good toughness, high heat resistance, strong adhesion and the like.
(2) Technical scheme
In a first aspect, the present invention provides a bio-based epoxy resin composition containing a silicon phenylene structure, which comprises the following raw materials, by mass:
100 parts of bio-based epoxy resin containing a silicon phenylene structure;
1-70 parts of a curing agent;
the structural formula of the bio-based epoxy resin containing the silicon phenylene structure is shown as a formula I-1:
the invention discloses a bio-based epoxy resin composition containing a silicon phenylene structure, which takes bio-based epoxy resin with a novel structure as matrix resin, the structure of the bio-based epoxy resin is eugenol bio-based epoxy resin containing a silicon phenylene structure, a main reaction functional group is eugenol epoxy group, and the introduction of the silicon phenylene structure in a molecular framework can greatly improve the intrinsic flame retardant property and the temperature resistance of the material. In addition, the introduction of heteroatom silicon reduces the viscosity of the system, so that the application requirements of different types of epoxy resins can be met by mixing the epoxy resin with other common epoxy resins.
The preparation method of the silicon-phenylene structure-containing bio-based epoxy resin comprises the following steps:
(1) mixing eugenol, epoxy chloropropane, solid alkali and a catalyst A under normal pressure, stirring for 1-2 hours at the low temperature of-20-0 ℃, then heating to 60-100 ℃, reacting for 1-10 hours, filtering, and removing impurities by rotary evaporation to obtain high-purity epoxidized eugenol;
the catalyst A is a halloysite nanotube which is immobilized with a mixture of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride;
(2) mixing the epoxidized eugenol prepared in the step (1), 1, 4-bis (dimethylsilyl) benzene and a catalyst B, and reacting to prepare the silicon-phenylene structure-containing bio-based epoxy resin.
In the preparation method, a halloysite nanotube immobilized with a mixture of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride is used as a catalyst for the first time, and a solid alkali adding method is adopted to carry out epoxidation reaction on eugenol and epoxy chloropropane. Experiments show that the self-made catalyst has excellent catalytic performance, most particularly can greatly reduce the content of hydrolyzable chlorine and the content of inorganic chlorine in epoxidized eugenol, and does not need a complex post-treatment process. In addition, under the condition of the self-made catalyst, the preparation process of the solid alkali-adding method can improve the yield to about 90 percent. In addition, the epoxidized eugenol with low content of hydrolyzable chlorine is used as a raw material to react with 1, 4-bis (dimethylsilyl) benzene to prepare the bio-based epoxy resin containing the silicon phenylene structure, and the cured silicon phenylene bio-based epoxy resin has excellent intrinsic flame retardant property, high heat resistance and bonding property.
In the step (1), the preparation steps of the catalyst A are as follows:
mixing aqueous solution of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride with halloysite nanotubes, treating mixed suspension for 0.5-1 hour by using a hypersonic dispersion machine, removing water by evaporation, and treating the rest substances in an ultrasonic oscillator for 0.1-0.5 hour at 70-110 ℃.
The Halloysite Nanotubes (HNTs) in the catalyst are natural nano materials with high strength and specific surface area, good adsorption performance and certain heat conduction capacity, have abundant Si-OH and Al-OH groups on the surface, are easy to modify and have hollow nano tubular structures.
Preferably, the tube length of the halloysite nanotube is 100-1000 nm, and the inner diameter of the tube is 0.1-100 nm.
The precursor is pretreated by a hypersonic dispersion machine and is further heated and reacted by an ultrasonic oscillation device, so that the formation of hydrogen bonds between hydroxyl on the surface of the halloysite nanotube and tetramethyl ammonium bromide and benzyl triethyl ammonium chloride is facilitated, and the subsequent catalytic effect is facilitated.
The concentration of the aqueous solution of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride is 10-1200 g/L, preferably 20-1200 g/L.
The mass ratio of the tetramethyl ammonium bromide to the benzyl triethyl ammonium chloride is 1: (1-5), preferably 1: (2-4).
The mass ratio of the total mass of solutes in the aqueous solution of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride to the halloysite nanotube is 1: (0.01 to 5), preferably 1: (0.05-5).
Experiments show that compared with a method of singly mixing tetramethyl ammonium bromide and benzyl triethyl ammonium chloride or simply mixing the tetramethyl ammonium bromide and the benzyl triethyl ammonium chloride with a halloysite nanotube as a catalyst, the method of using the halloysite nanotube immobilized with the tetramethyl ammonium bromide and the benzyl triethyl ammonium chloride as the catalyst can further improve the yield of an epoxidation product and reduce the content of hydrolyzable chlorine in a final product, and compared with a solution alkali adding method, the preparation process using a solid alkali adding method greatly simplifies process steps and improves the yield. The reason for analyzing the method is probably that the stable hydrogen bond can be formed between the treated surfaces of the halloysite nanotubes and tetramethyl ammonium bromide and benzyl triethyl ammonium chloride, and the catalytic efficiency is greatly improved due to the high specific surface area in the pore channels.
If only the solid addition and subtraction method is adopted, but the catalyst A is not adopted, experiments show that the highest yield can only reach about 70 percent, and the content of hydrolyzable chlorine is more than 200 ppm; if only the catalyst A is used, but the solid addition and subtraction method is not used, experiments show that the content of hydrolyzable chlorine can only be controlled to be about 80ppm at the lowest, and the further reduction is difficult.
Experiments show that the content of hydrolyzable chlorine in the prepared epoxidized eugenol can be controlled below 70ppm only by simultaneously adopting the solid addition and subtraction method and the optimized catalyst A, and the yield is stabilized above 80 percent and can be up to 90 percent.
If tetramethylammonium bromide and benzyltriethylammonium chloride supported on halloysite nanotubes are replaced with another common phase transfer catalyst (dodecyltriethylammonium bromide). It was found by experiments that the hydrolyzable chlorine of the final product could not be reduced significantly.
If the halloysite nanotubes are replaced by a carrier with a nano-porous structure, such as carbon nanotubes, which is common in the catalyst field. Experiments show that the content of the hydrolysable chlorine in the final product is not obviously different from the content of the final product which directly adopts tetramethyl ammonium bromide and benzyl triethyl ammonium chloride.
Therefore, the solid alkali adding method and the self-made catalyst A have mutual synergistic effect, the combination has specificity, the content of hydrolyzable chlorine can be obviously reduced, and the difference of the mixing mode and the components can obviously influence the realization of the technical effect.
In the step (1), the solid alkali is at least one of sodium hydroxide, potassium hydroxide and magnesium hydroxide, preferably at least one of sodium hydroxide and potassium hydroxide.
In the step (1), the mol ratio of the eugenol to the epichlorohydrin to the solid alkali is 1: (5-10): (1-5), preferably 1: (5-8): (2-5).
The content of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride in the catalyst A is 1-10% of the total mass of the eugenol, the epoxy chloropropane and the solid alkali, and the preferable content is 1-9%.
In the step (2), the reaction is a hydrosilylation reaction, and the hydrosilylation reaction conditions are as follows:
under the protection of nitrogen, adding epoxy eugenol, 1, 4-bis (dimethylsilyl) benzene and a catalyst B into a solvent, stirring at room temperature for 20-40 min, heating to 60-100 ℃ for reaction for 2-4 h, adding a proper amount of adsorbent into a reaction system after the reaction is finished, stirring at room temperature for 30min, standing for 1-2 h for adsorbing the catalyst, centrifuging the system at high speed to remove precipitates, and finally performing rotary evaporation to obtain the bio-based epoxy resin containing the silylene structure.
The molar ratio of the epoxidized eugenol to the 1, 4-bis (dimethylsilyl) benzene is 2: 1.
Preferably, the catalyst B is a homogeneous transition metal catalyst such as at least one of platinum, palladium, rhodium, nickel, organometallic complexes thereof, and the like, preferably at least one of platinum and organometallic complexes such as Karstedt's catalyst.
The dosage of the catalyst B is 10-30 ppm, preferably 10-20 ppm of the total mass of the epoxidized eugenol and the 1, 4-bis (dimethylsilyl) benzene.
The solvent is at least one selected from toluene, methanol, acetone, tetrahydrofuran, etc., and is preferably toluene.
The dosage of the solvent is 2-5 times of the total mass of the reactants, and preferably 2-4 times.
The adsorbent is selected from at least one of alumina, activated carbon, graphite, polyacrylamide, carbon molecular sieve and the like, and is preferably selected from at least one of graphite and carbon molecular sieve.
The dosage of the adsorbent is 0.1-5 times of the total mass of the reactants, and preferably 1-4 times.
Preferably, the epoxy resin composition containing a silicon phenylene structure comprises the following raw materials in parts by mass:
100 parts of bio-based epoxy resin containing a silicon phenylene structure;
1-70 parts of nitrile rubber;
1-30 parts of a curing agent.
The nitrile rubber is carboxyl-terminated nitrile rubber, has a molecular weight of 20000-500000, and can be specifically selected from nitrile rubber NBR4005 or N21.
The curing agent is selected from curing agent types commonly used in the field, and comprises at least one of aliphatic amine curing agent, aromatic amine curing agent (such as diaminodiphenylmethane), dicyandiamide curing agent (such as dicyandiamide), acid anhydride curing agent (such as methyl nadic anhydride), polyether amine curing agent (such as polyether amine T403), phenolic aldehyde amine curing agent, polyamide curing agent and the like.
Further preferably, the epoxy resin composition containing a silicon phenylene structure comprises the following raw materials in parts by mass:
100 parts of bio-based epoxy resin containing a silicon phenylene structure;
20-50 parts of nitrile rubber;
5-20 parts of a curing agent.
According to specific performance requirements, a curing agent accelerator and a coupling agent can be added into the epoxy resin composition containing the silicon phenylene structure.
The accelerator is selected from the group of accelerators commonly used in the art, including alcohol amine based accelerators (e.g., triethanolamine), imidazole based accelerators (e.g., 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2-methylimidazole), phenol based accelerators (e.g., tetrachlorobisphenol a, 2,4, 6-tris (dimethylaminomethyl) phenol), and mixtures of the foregoing in any proportion.
The coupling agent is a silane coupling agent or a titanate coupling agent.
In a second aspect, the invention provides an application of a bio-based epoxy resin composition containing a silicon phenylene structure in preparing an epoxy resin adhesive film.
In a third aspect, the invention provides an epoxy resin adhesive film, which is obtained by mixing and coating a bio-based epoxy resin composition containing a silicon phenylene structure.
The preparation method of the epoxy resin adhesive film comprises the following steps:
the epoxy resin composition is prepared by blending the raw materials, coating the mixture on release paper, heating, curing, rolling, compounding and rolling;
or the epoxy resin composition is prepared by mixing the raw materials, coating the mixture on a carrier, heating and curing the carrier, and then pressing and compounding the carrier and an isolation paper roll.
The carrier is at least one selected from glass fiber cloth, nylon gauze, polyester gauze and the like.
Therefore, the epoxy resin adhesive film disclosed by the invention can only comprise a bare film obtained by mixing and coating the bio-based epoxy resin composition containing the silicon phenylene structure, and can also comprise an adhesive film obtained by mixing and coating the bio-based epoxy resin composition containing the silicon phenylene structure and taking glass fiber cloth, nylon gauze and polyester gauze as carriers.
The thickness of the epoxy resin adhesive film is 1-500 μm, preferably 1-300 μm.
(3) Advantageous effects of the invention
The bio-based epoxy resin composition containing the silicon phenylene structure provided by the invention takes a bio-based epoxy resin with a novel structure prepared by a special catalyst and a solid alkali adding method as a matrix, the bio-based epoxy resin is eugenol bio-based epoxy resin containing the silicon phenylene structure, a main reaction functional group is eugenol epoxy group, and the introduction of the silicon phenylene structure in a molecular framework can greatly improve the intrinsic flame retardant property and the temperature resistance of the material. In addition, the introduction of heteroatom silicon reduces the viscosity of the system. The epoxy resin composition with the epoxy resin as the matrix resin can realize the flame retardance of the body without adding a flame retardant, so that the epoxy resin adhesive film prepared from the composition has outstanding flame retardance, toughness, temperature resistance and bonding performance, is suitable for structural adhesives, and is particularly suitable for bonding the surfaces of metals, composite materials and plastics.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments of the present invention will be briefly described below.
FIG. 1 shows the NMR spectrum of a bio-based epoxy resin (shown in structural formula I-1) containing a silicon phenylene structure prepared by an example of the present invention.
Detailed Description
The embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following detailed description of the embodiments and the accompanying drawings are intended to illustrate the technical solutions of the present invention, but should not be construed to limit the scope of the present invention, i.e., the present invention is not limited to the described embodiments, and covers any modifications, substitutions and improvements of the raw materials without departing from the spirit of the present invention.
The raw materials, equipments and the like used in the following examples, comparative examples and experimental examples are commercially available.
Example 1
In this embodiment, the bio-based epoxy resin composition containing a silicon phenylene structure comprises, by mass:
the preparation method of the bio-based epoxy resin containing the silicon phenylene structure in the embodiment comprises the following steps:
(1) mixing 2g of tetramethylammonium bromide and 4g of benzyltriethylammonium chloride aqueous solution (solution concentration is 20g/L, 300mL) with 30g of halloysite nanotubes, treating the mixed suspension with a hypersonic dispersion machine for 1 hour, removing water by evaporation, placing the remaining substance in an ultrasonic oscillator, and treating at 100 ℃ for 0.5 hour to obtain the halloysite nanotubes (namely catalyst A) immobilized with the mixture of tetramethylammonium bromide and benzyltriethylammonium chloride.
(2) At normal pressure, eugenol, epichlorohydrin and solid alkali are mixed according to the mol ratio of 1: 5: 3, mixing the components together, simultaneously adding a catalyst A (wherein the content of tetramethylammonium chloride and benzyltriethylammonium chloride is 6 percent of the total mass of the eugenol, the epichlorohydrin and the solid alkali), stirring the mixture for 1 hour at the temperature of minus 20 ℃, then heating the mixture to 90 ℃ for reaction for 4 hours, filtering the mixture, and performing rotary evaporation to remove impurities to obtain the epoxidized eugenol. The yield (based on the phenolic hydroxy compound) was 90%. Referring to the GB/T13657 Standard test for general epoxy resins, the epoxidized eugenol prepared in this example has a hydrolyzable chlorine content of 65ppm and an inorganic chlorine content of 5 ppm.
(3) Under the protection of nitrogen, the epoxidized eugenol and the 1, 4-bis (dimethylsilyl) benzene are mixed according to the molar ratio of 2:1, adding the mixture into 400ml of toluene, adding 20ppm of Karstedt catalyst, stirring at room temperature for 30min, heating to 100 ℃ for reaction for 3.5 h, cooling to room temperature, adding graphite (2 times of the total mass of reactants) in proportion, stirring at room temperature for 30min, standing for 2 h, performing high-speed centrifugation to extract supernatant, and distilling to obtain the bio-based epoxy resin containing the silicon phenylene structure. According to nuclear magnetic tests, the structural formula of the bio-based epoxy resin containing the silicon phenylene structure prepared in the embodiment is shown as the formula I-1.
The preparation method of the epoxy resin adhesive film in the embodiment comprises the following steps:
100 parts of the prepared bio-based epoxy resin containing the silicon phenylene structure, 10 parts of dicyandiamide, 0.3 part of 2-methyl-4-ethylimidazole and 30 parts of nitrile butadiene rubber (NBR4005) are mixed for 30min by using a three-dimensional blender, coated on a polyester screen by a glue spreader, the thickness of the glue film is controlled to be 300 mu m, then the glue film is placed into a 150 ℃ oven to be heated for 5 min to form a pre-cured glue film, and then the pre-cured glue film and an isolation paper are pressed, compounded and rolled to obtain the epoxy glue film. The relevant properties are detailed in table 1.
Example 2
In this embodiment, the bio-based epoxy resin composition containing a silicon phenylene structure comprises, by mass:
the preparation method of the epoxy resin adhesive film in the embodiment comprises the following steps:
100 parts of the bio-based epoxy resin containing a silicon phenylene structure prepared in the example 1, 28 parts of diaminodiphenylmethane, 0.5 part of accelerator 2-methylimidazole and 30 parts of nitrile butadiene rubber (NBR4005) are mixed by using a three-dimensional blender for 30min, coated on a polyester screen by a glue spreader, the thickness of the glue film is controlled to be 300 mu m, and then the glue film is put into a 180 ℃ oven to be heated for 3 min to form a pre-cured glue film, and then the pre-cured glue film and an isolation paper roll are pressed and compounded to be rolled to obtain the epoxy resin glue film. The relevant properties are detailed in table 1 below.
Example 3
In this embodiment, the bio-based epoxy resin composition containing a silicon phenylene structure comprises, by mass:
the preparation method of the bio-based epoxy resin containing the silicon phenylene structure in the embodiment comprises the following steps:
(1) 2g of tetramethylammonium bromide and 6g of a benzyltriethylammonium chloride aqueous solution (concentration: 100g/L, 50mL) were mixed with 20g of a halloysite nanotube, the mixed suspension was treated with a hypersonic dispersion machine for 1 hour, water was removed by evaporation, and the remaining material was put in an ultrasonic oscillator and treated at 110 ℃ for 0.5 hour to obtain a halloysite nanotube (i.e., catalyst A) immobilized with a mixture of tetramethylammonium bromide and benzyltriethylammonium chloride.
(2) At normal pressure, eugenol, epichlorohydrin and solid alkali are mixed according to the mol ratio of 1: 5: 3, mixing the components together, simultaneously adding a catalyst A (wherein the content of tetramethylammonium chloride and benzyltriethylammonium chloride is 6 percent of the total mass of the eugenol, the epichlorohydrin and the solid alkali), stirring the mixture for 1 hour at the temperature of minus 20 ℃, then heating the mixture to 85 ℃ for reaction for 4 hours, filtering the mixture, and performing rotary evaporation to remove impurities to obtain the epoxidized eugenol. The yield (based on the phenolic hydroxy compound) was 92%. Referring to the GB/T13657 Standard test for general epoxy resins, the epoxidized eugenol prepared in this example has a hydrolyzable chlorine content of 60ppm and an inorganic chlorine content of 6 ppm.
(3) Under the protection of nitrogen, the epoxidized eugenol and the 1, 4-bis (dimethylsilyl) benzene are mixed according to the molar ratio of 2:1, adding the mixture into 300ml of toluene, adding 20ppm of Karstedt catalyst at the same time, stirring the mixture at room temperature for 30min, heating the mixture to 100 ℃ for reaction for 3.5 h, cooling the mixture to room temperature, adding graphite (2 times of the total mass of reactants) in proportion, stirring the mixture at room temperature for 30min, standing the mixture for 2 h, performing high-speed centrifugation to extract supernatant, and distilling the supernatant to obtain the bio-based epoxy resin containing the silicon phenylene structure. According to nuclear magnetic tests, the structural formula of the bio-based epoxy resin containing the silicon phenylene structure prepared in the embodiment is shown as the formula I-1.
The preparation method of the epoxy resin adhesive film in the embodiment comprises the following steps:
mixing 100 parts of the prepared bio-based epoxy resin containing the silicon phenylene structure, 20 parts of methyl nadic anhydride, 1 part of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) and 30 parts of nitrile rubber (N21) for 30min by using a three-dimensional blender, coating the mixture on release paper by using a glue spreader, controlling the thickness of the glue film to be 300 mu m, then putting the glue film into a 160 ℃ oven, heating for 6 min to form a pre-cured glue film, and then laminating and rolling the pre-cured glue film and the release paper to obtain the epoxy glue film. The relevant properties are detailed in table 1.
Example 4
In this embodiment, the bio-based epoxy resin composition containing a silicon phenylene structure comprises, by mass:
the preparation method of the epoxy resin adhesive film in the embodiment comprises the following steps:
taking 100 parts of the bio-based epoxy resin containing a silicon phenylene structure prepared in the example 3, 20 parts of polyetheramine (T403), 0.3 part of accelerator 2-methylimidazole and 30 parts of nitrile rubber (N21), mixing for 30min by using a three-dimensional blender, coating the mixture on release paper by using a glue spreader, controlling the thickness of the glue film to be 300 mu m, then placing the release paper into a 120 ℃ oven to heat for 2 min to form a pre-cured glue film, and then pressing, compounding and rolling the pre-cured glue film and the release paper to obtain the epoxy resin glue film. The relevant properties are detailed in table 1 below.
Comparative example 1
The preparation method of the epoxy resin adhesive film in the comparative example comprises the following steps:
(1) the raw materials and process parameters for preparing the epoxidized eugenol are completely the same as those in example 1, and the difference is only that tetramethyl ammonium bromide and benzyl triethyl ammonium chloride are directly added as catalysts. The yield (calculated as phenolic hydroxy compound) was 70%; the test shows that the prepared epoxidized eugenol has the hydrolysable chlorine content of 650ppm and the inorganic chlorine content of more than 700 ppm.
(2) The preparation and curing processes of the bio-based epoxy resin containing the silicon phenylene structure are completely the same as those in the example 1, and the prepared bio-based epoxy resin containing the silicon phenylene structure contains a large number of epoxy groups which are not closed. The epoxy resin adhesive film is prepared by using the epoxy resin as matrix resin and adopting the raw material composition and the preparation process which are completely the same as those in the embodiment 1, and all performance indexes of the epoxy resin adhesive film are listed in the following table 2.
Comparative example 2
The preparation method of the epoxy resin adhesive film in the comparative example comprises the following steps:
(1) the raw materials and technological parameters for preparing the epoxidized eugenol are completely the same as those in the example 1, and the difference is that the solid alkali with the same content is prepared into an aqueous solution by adopting a liquid alkali adding method, and the aqueous solution is slowly dripped into a reaction system twice. The yield (calculated as phenolic hydroxy compound) was 65%; tests show that the prepared epoxidized eugenol has the hydrolysable chlorine content of 300ppm and the inorganic chlorine content of more than 400 ppm.
(2) The preparation and curing processes of the bio-based epoxy resin with the silicon-containing phenylene structure are completely the same as those in the example 1, and the prepared bio-based epoxy resin with the silicon-containing phenylene structure contains an epoxy group which is not closed. The epoxy resin adhesive film is prepared by using the epoxy resin as matrix resin and adopting the raw material composition and the preparation process which are completely the same as those in the embodiment 1, and all performance indexes of the epoxy resin adhesive film are listed in the following table 2.
Comparative example 3
The preparation method of the epoxy resin adhesive film in the comparative example comprises the following steps:
(1) the raw materials and process parameters for preparing the epoxidized eugenol are the same as those in example 1, except that dodecyltriethylammonium bromide is directly added as a catalyst. Tests show that the prepared epoxidized eugenol has the hydrolysable chlorine content of 1200ppm and the inorganic chlorine content of more than 1500 ppm.
(2) The preparation and curing processes of the bio-based epoxy resin containing the silicon phenylene structure are completely the same as those in the example 1, and the prepared bio-based epoxy resin containing the silicon phenylene structure contains a large number of epoxy groups which are not closed. The epoxy resin adhesive film is prepared by using the epoxy resin as matrix resin and adopting the raw material composition and the preparation process which are completely the same as those in the embodiment 1, and all performance indexes of the epoxy resin adhesive film are listed in the following table 2.
Comparative example 4
The preparation method of the epoxy resin adhesive film in the comparative example comprises the following steps:
(1) the raw materials and process parameters for preparing the epoxidized eugenol are completely the same as those in the example 1, and the difference is that the catalyst is prepared by simply blending tetramethyl ammonium bromide, benzyl triethyl ammonium chloride and halloysite nanotubes. Tests show that the prepared epoxidized eugenol has the hydrolysable chlorine content of 700ppm and the inorganic chlorine content of more than 750 ppm.
(2) The preparation and curing processes of the bio-based epoxy resin containing the silicon phenylene structure are completely the same as those in the example 1, and the prepared bio-based epoxy resin containing the silicon phenylene structure contains a large number of epoxy groups which are not closed. The epoxy resin adhesive film is prepared by using the epoxy resin as matrix resin and adopting the raw material composition and the preparation process which are completely the same as those in the embodiment 1, and all performance indexes of the epoxy resin adhesive film are listed in the following table 2.
Comparative example 5
The preparation method of the epoxy resin adhesive film in the comparative example comprises the following steps:
(1) the raw materials and process parameters for preparing epoxidized eugenol are identical to those of example 1, except that the halloysite nanotubes in the catalyst are replaced by multiwalled carbon nanotubes, and the preparation steps are the same as those of catalyst A. Tests show that the prepared epoxidized eugenol has the hydrolysable chlorine content of 800ppm and the inorganic chlorine content of more than 800 ppm.
(2) The preparation and curing processes of the bio-based epoxy resin containing the silicon phenylene structure are completely the same as those in the example 1, and the prepared bio-based epoxy resin containing the silicon phenylene structure contains a large number of epoxy groups which are not closed. The epoxy resin adhesive film is prepared by using the epoxy resin as matrix resin and adopting the raw material composition and the preparation process which are completely the same as those in the embodiment 1, and all performance indexes of the epoxy resin adhesive film are listed in the following table 2.
Comparative example 6
In the comparative example, the epoxy resin composition comprises the following raw materials in parts by mass:
the preparation method of the epoxy resin adhesive film in the comparative example comprises the following steps:
taking 100 parts of E51 epoxy resin, 10 parts of dicyandiamide, 0.3 part of 2-methyl-4-ethylimidazole and 35 parts of nitrile butadiene rubber (NBR4005), mixing for 30min by using a three-dimensional blender, coating the mixture on a nylon gauze by using a glue spreader, controlling the thickness of the glue film to be 100 mu m, then putting the glue film into a 150 ℃ oven to heat for 5 min to form a pre-cured glue film, and then pressing and compounding and rolling the pre-cured glue film and an isolation paper roll to obtain the epoxy resin glue film. The relevant properties are detailed in table 2 below.
Comparative example 7
In the comparative example, the epoxy resin composition comprises the following raw materials in parts by mass:
the preparation method of the epoxy resin adhesive film in the comparative example comprises the following steps:
100 parts of E44 epoxy resin, 28 parts of diaminodiphenylmethane, 0.5 part of accelerator 2-methylimidazole and 30 parts of nitrile butadiene rubber (NBR4005) are mixed for 30min by using a three-dimensional blender, coated on a polyester screen by a glue spreader, controlled in thickness of 200 mu m, then placed in an oven at 180 ℃ for heating for 3 min to form a pre-cured glue film, and then pressed and compounded with an isolation paper roll for rolling to obtain the epoxy resin glue film. The relevant properties are detailed in table 2 below.
Examples of the experiments
The epoxy resin adhesive films in the examples and the comparative examples are taken for performance test, and the test method is as follows:
(1) the adhesive strength was tested according to GB/T7124 (adhesive tensile shear Strength test method), which comprises applying an adhesive film to the surface of a patch, curing at 80 ℃ for 1 hour, curing at 150 ℃ for 2 hours and curing at 180 ℃ for 0.5 hour.
(2) The limiting oxygen index is determined according to ASTM D2863 test standards.
(3) The heat resistance adopts a TG209 thermogravimetric analyzer (TGA) of Germany NETZSCH company, the test condition is a nitrogen atmosphere, the heating rate is 10 ℃/min, and the test sample is about 13mg from 100 ℃ to 800 ℃. The test results are detailed in tables 1 and 2 below.
Table 1 shows the results of the performance test of the epoxy resin film in the examples
| Performance of | Example 1 | Example 2 | Example 3 | Example 4 |
| Iron sheet bonding Strength (MPa) | 14.4 | 16.8 | 15.1 | 14.2 |
| Iron sheet adhesion modulus (MPa) | 3050 | 3650 | 3560 | 3100 |
| Limiting Oxygen Index (LOI) | 31 | 33 | 32 | 30 |
| T5％(℃) | 307 | 314 | 310 | 308 |
TABLE 2 results of performance test of epoxy resin adhesive film in comparative example
The above description is only an example of the present invention, and does not limit the protection scope of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the technical spirit of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A bio-based epoxy resin composition containing a silicon phenylene structure is characterized in that: the raw materials comprise the following components in percentage by mass:
100 parts of bio-based epoxy resin containing a silicon phenylene structure;
1-70 parts of a curing agent;
the structural formula of the bio-based epoxy resin containing the silicon phenylene structure is shown as a formula I-1:
2. the silicon-phenylene structure-containing bio-based epoxy resin composition according to claim 1, wherein: the raw materials comprise the following components in percentage by mass:
100 parts of bio-based epoxy resin containing a silicon phenylene structure;
1-70 parts of nitrile rubber;
1-30 parts of a curing agent.
3. The silicon-phenylene structure-containing bio-based epoxy resin composition according to claim 1, wherein: the nitrile rubber is carboxyl-terminated nitrile rubber, and the molecular weight is 20000-500000;
the curing agent is at least one selected from aliphatic amine curing agents, aromatic amine curing agents, dicyandiamide curing agents, acid anhydride curing agents, polyether amine curing agents, phenolic aldehyde amine curing agents and polyamide curing agents.
4. The silicon-phenylene structure-containing bio-based epoxy resin composition according to claim 1, wherein: the preparation method of the silicon-phenylene structure-containing bio-based epoxy resin comprises the following steps:
(1) mixing eugenol, epoxy chloropropane, solid alkali and a catalyst A under normal pressure, stirring for 1-2 hours at the low temperature of-20-0 ℃, then heating to 60-100 ℃, reacting for 1-10 hours, filtering, and removing impurities by rotary evaporation to obtain epoxidized eugenol;
the catalyst A is a halloysite nanotube which is immobilized with a mixture of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride;
(2) mixing the epoxidized eugenol prepared in the step (1), 1, 4-bis (dimethylsilyl) benzene and a catalyst B, and reacting to prepare the silicon-phenylene structure-containing bio-based epoxy resin.
5. The silicon-phenylene structure-containing bio-based epoxy resin composition according to claim 4, wherein: in the step (1), the mol ratio of the eugenol to the epichlorohydrin to the solid alkali is 1: (5-10): (1-5);
the content of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride in the catalyst A is 1-10% of the total mass of the eugenol, the epoxy chloropropane and the solid alkali.
6. The silicon-phenylene structure-containing bio-based epoxy resin composition according to claim 4, wherein: in the step (1), the preparation steps of the catalyst A are as follows:
mixing aqueous solution of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride with halloysite nanotubes, treating the mixed suspension by using a hypersonic dispersion machine for 0.5-1 hour, removing water by evaporation, and treating the rest in an ultrasonic oscillator for 0.1-0.5 hour at 70-110 ℃;
the concentration of the aqueous solution of the tetramethyl ammonium bromide and the benzyltriethyl ammonium chloride is 10-1200 g/L;
the mass ratio of the tetramethyl ammonium bromide to the benzyl triethyl ammonium chloride is 1: (1-5);
the mass ratio of the total mass of solutes in the aqueous solution of tetramethyl ammonium bromide and benzyl triethyl ammonium chloride to the halloysite nanotube is 1: (0.01-5).
7. Use of the silicon-phenylene structure-containing bio-based epoxy resin composition according to any one of claims 1 to 6 in preparation of an epoxy resin adhesive film.
8. An epoxy resin adhesive film is characterized in that: the epoxy resin adhesive film is obtained by mixing and coating a silicon-phenylene structure-containing bio-based epoxy resin composition.
9. The epoxy adhesive film according to claim 8, wherein: the preparation method of the epoxy resin adhesive film comprises the following steps:
the epoxy resin composition is prepared by blending the raw materials, coating the mixture on release paper, heating, curing, rolling, compounding and rolling;
or the epoxy resin composition is prepared by mixing the raw materials, coating the mixture on a carrier, heating and curing the carrier, and then pressing and compounding the carrier and an isolation paper roll.
10. The epoxy adhesive film according to claim 9, wherein: the carrier is selected from at least one of glass fiber cloth, nylon gauze and polyester gauze;
the thickness of the epoxy resin adhesive film is 1-500 mu m.
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